Process for preparing acylated amine-cs2 compositions and products



I imparting several desirable properties to an oil.

United States Patent 3,200,107 PROCESS FOR PREPARING ACYLATED AMlNE-CS COMPOSITIONS AND PRODUCTS William M. Le Suer, Cleveland, Ohio, assignor to The ldtlilbrizol Corporation, Wicklilfe, Ohio, a corporation of No Drawing. Filed June 12, 1961, Ser. No. 116,289 17 Claims. (Cl. 260-432) 1 This invention relates to sulfurand nitrogen-containing compositions and in a more particular sense it relates to sulfunand nitrogen-containing compositions adapted for use as additives in hydrocarbon oils. This invention relates also to hydrocarbon oils, especially lubricating oil compositions.

The problem of deterioration of hydrocarbon oils has been the cause of principal concern in the formulation of hydrocarbon oil compositions such as fuels and lubricating compositions. Deterioration of hydrocarbon oils results in the formation of products which are corrosive to the metal surfaces with which the oils come into contact. It results also in the formation of products which have a tendency to agglomerate to form sludge and varnish-like deposits.

In recent years it has been a common practice to incorporate into hydrocarbon oils chemical additives which are capable of inhibiting the deterioration of oil and the formation of these harmful deposits. Such additives have generally been classified into three principal groups according to the manner in which they function to improve the hydrocarbon oil. One group of such additives are the oxidation inhibitors which function to stabilize the oil against oxidative degradation. Another group of such additives are the corrision inhibitors which counteract the corrosiveness of the products of oil degradation or passivate the metal surfaces against the corrosive action of such products. Still another group of such additives are the detergents or dispersing agents which function to maintain products of oil degradation in dispersion in the oil phase and to prevent the deposition of sludge and varnish.

Two or more such additives are often needed in a hydrocarbon oil to stabilize the oil against formation of harmful degradation products. The incorporation in an oil, however, of several different types of additives not only is costly, but is also dependent upon the compatibility of the additives with one another. Thus, it is known that additives which are effective separately may not be used in combination because of their incompatibility. A great deal of eifort has recently been devoted to the development of so-called multi-functional additive, i.e., an additive which, by itself, is capable of It will be readily appreciated that the use of such additive is highly advantageous from the standpoint of both economy and convenience.

It is, accordingly, an object of this invention to provide novel compositions of matter. 7

It is also an object of this invention to provide compositions adapted for use as additives in hydrocarbon oils.

It is also an object of this invention to provide compositions use-ful as corrosion and oxidation inhibitors in hydrocarbon oils.

3,200,107 Patented Aug. 10, 1965 It is also an object of this invention to provide compositions useful as detergents in hydrocarbon oils.

It is also an object of this invention to provide com positions useful as both detergent additives and oxidation and corrosion inhibitors in hydrocarbon oils.

It is also an object of this invention to provide improved hydrocarbon oils.

It is also an object of this invention to provide improved fuel ompositions.

It is also an object of this invention to provide improved lubricating compositions.

These and other objects are attained in accordance with this invention by providing a process for preparing sulfurand nitrogen-containing compositions which comprises reacting at a temperature above about C. 1.0 mole of an alkylene amine with at least about 0.5 equivalent of carbon disulfide and at least about 1.0 equivalent of a substantially hydrocarbon-substituted dicarboxylic acid having at least about 12 aliphatic carbon atoms in the hydrocarbon radical, and removing the water formed by the reaction.

The alkylene amines useful in the above process are the plyamines conforming for the most part to the structure in which n is an integer preferably less than about 8. The alkylene amines include, for example, ethylene amines, propylene amines, butylene amines, trimethylene amines, tetramethylene amines, and also the cyclic homologues of such polyamines, e.g., piperazines. Specific examples of the alkylene amines are ethylene diamine, diethylene triamine, triethylene teteramine, propylene diamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene tetramine, di(trimethylene) triamine, N-2-aminoethyl-piperazine, octamethylene diamine, etc. The ethylene amines are especially useful. They are described in some detail under the heading ethylene amines in Encyclopedia of Chemical Technology, Kirk and Othmer, volume 5, pages 898-905, Interscience Publishers, New York (1950). Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia. This reaction results in the production of somewhat complex mixtures of alkylene amines including cyclic condensation products such as piperazines and these mixtures find use in the process of this invention. On the other hand, quite satisfactory products may be obtained also by the use of pure alkylene amines. An especially useful alkylene amine for reasons of economy as Well as effectiveness of the products derived therefrom is a mixture of ethylene amine prepared by the reaction of ethylene chloride and ammonia having a composition which corresponds to that of tetraethylene pentamine. This is available in the trade under the trade name Polyamine H.

The term dicarboxylic acid is used in the specification and the claims of this invention in a generic sense to include both the acid and the anhydride of the acid. In most instances the anhydride is preferred for use because of its greater reactivity. The substantially hydrocarbonsubstituted dicarboxylic acids useful herein comprise principally the substituted succinic acids and anhydrides, although other dicarboxylic acids such as substituted malonic acids, glutaric acids, adipic acids, etc likewise are contemplated for use herein. The substantially hydrocarbon radical in such acids should cont-am at least about 12 aliphatic carbon atoms in order to impart sufficient oil solubility. It may also contain a polar substituent such as chlor-o, bromo, nitro, alkoxy, or phenoxy radical.

The substantially hydrocarbon-substituted succinic acids may be prepared by reacting maleic anhydride with an olefin or a chlorinated hydrocarbon. The reactlon involves merely heating the reactants to a temperature above about 100 C. and the product is an HlkIlYlSllCClIllC anhydride. The alkenyl group may be hydrogenerated anhydride. The alke'nyl group may be hydrogenated the corresponding acid by treatment with water or steam. The most common sources of the hydrocarbon radicals in such acids are olefin polymers such as polyethylene, polypropene, polyisobutene, etc. having molecular we1ghts above about 150. A particularly preferred polyolefin for this use is polyisobutene.

The use of olefin polymers having molecular weight above about 700 has been found to result in products which are especially useful for the purpose of this invention and is therefore preferred. Higher molecular weight olefin polymers, that is, those having molecular weights above about 50,000 or 100,000, have been found to impart also viscosity index improving propertiesto the products obtained by the process of this invention. The use of such, higher molecular weight olefin polymers is in many instances desirable. Copolymers of aliphatic olefins with a small amount, i.e., less than about 5% by weightiof aroma-tic olefins such as styrene or diolefins such as isoprene, chloroprene, butadiene likewise are contemplated for use herein. Other sources of the hydrocarbon substituent include petroleum fractions such as' mineral oil, waxes, still bottoms, etc.

The reaction which characterizes the process of this invention involves the acylation of at least one nitrogen atom. of the alkylene amine with an acid radical of the dicarb-oxylic acid. It involves also the reaction of at least 0.5 equivalent of the alkylene amine with carbon disulfide. The acylation requires a temperatureof at least about 80 C. and is accompanied by the formation of one mole of water from each equivalent of the acid radical. The product of the acylation is thereforesubstantially nonacidic and is believed to comprise predominantly an amide or an imide and may include cyclic amide and polyamide linkages. A small amount of amine carboxylate salts and imidazolines may also be formed but these do not amount to an appreciable proportion of the product.

The exact nature of the reaction involving the amine with carbon disulfide is not known, although it appears that the stoichiometry of the reaction requires one equivalent (i.e., one-halfmole) of the carbon disulfide for one equivalent of the amine. The reaction is exothermic and takes place readily uponmixing the amine with carbon disulfide. Although substantially all of the sulfur from the carbon disulfide appears in the product, one-half of this sulfur is so reactive as to be readily removed upon heating at a temperature above about 70 C. The precise structure .of either product is not known, i.e., the one obtained simply by mixing the amine and carbon disulfide and the one obtained by heating such a mixture above about 70 C. Both, however, are contemplated as being within the scope of this invention.

A plausible explanation for the formation of the products of this process is found in the following equations, Where R is a hydrocarbon radical and R is an alkylene radical? Amide-thiourea the above equations are no more than illustrative. They are based upon the st-oichiometry indicated by suitable proportions of reactants. The complexity of the process is shown by theQfa'ct that the products may contain substantial proportions of 'imide, cyclic amide, and polyamide linkages as well as linkages other than the dithi-ocarbamic acid-amine or thiour'ea types, It will be noted also that the above equations are accurate only when the amine and acid are reacted together. first, and then the carbon dissulfide; I I

The process of this invention may be carried out by mixing the reactants in any order. All three reactants may be mixed at room temperature and heated to a temperature above about 80 C. to eifect' acylation. The reaction may likewise be carried out by first reacting the amine with carbon disulfide and'then acylating the intermediate product With the .dicarboxylic acid, or by acylating the amine with the dicarboxylic acid and then reacting the acylated amine with carbon disulfide. This lastmentioned mode of carrying out the process is preferred because the products obtained have been found to be especially useful for the purpose of this invention. The preferred temperature for carrying out. theacylation is between about 150 C. and 250 C.

As indicated previously the acylation is accompanied by the formation of water. The removal of the water formed can be effected by heating the reaction mixture to 100 C. or higher. It may be facilitated by blowing the reaction mixture with an inert gas such as nitrogen duringsuch heating. It may befacilitated also by the use in the reaction mixture of "an inert solvent which forms a co-distillable azeotropic mixture with water. EX- amples of such solvents are benzene, n-hexane, toluene, Xylene, etc. Theuse of such solvents permits the removal of water at a substantially lower temperature, e.g., -C.

The relative proportions of reactants to be used in the process are, based: upon the stoichiometry of the reaction involved in the processand the utility of; the products obtained therefrom for the purpose of this invention. The minimum amounts of the dicarboxylic acid andthe car bon disulfide to be used are 1 equivalent of the dicarboxylic acid ('1 mole contains 2 equivalents) and about 0.5 equivalent of the carbon sulfide (1 mole contains 2 equivalents) for each rnoleof the alkyleneamine used. The maximum amounts of these two reactants to be used are based on the total number of equivalents of the alkylene amine used. In this respect, it will be noted that 1 mole of thealkylene amine contains as many equivalents as there are nitrogen atoms in the molecule.

Thus, the maximum combined equivalents of dicarbox ylic acid and carbon disulfide which can react with one mole of alkylene amine is equal to the number. of nitro gen atoms in thelalkylene amine molecule. If anexcess; of carbon disulfide or dicarboxylic acid is used, thisexcess will not take part in the reaction and consequently such excess has littlebeneficial effect. On'flthe other hand, if the total amount of the :dicarboirylic acid and the carbon disulfide used is less than the maximum amount, the products will contain un-reacted free amino nitrogen atoms. Such products have been found to be useful in this invention. It has also been found that the products having particular usefulness in this invention are those obtained by the use of dicarboxylic acid and carbon disulfide in relative amounts within the limits of ratio of equivalents from about 1:3 to about 3:1. A specific example illustrating the limits of the relative proportions of the reactants is as follows: one mole of a tetraalkylene pentamine is reacted with from 1 to 4.5 equivalents, preferably from 1 to 3 equivalents, of dicarboxylic acid and from about 0.5 to 4 equivalents, preferably from 1 to 3 equivalents, of carbon disulfide.

EXAMPLE 1 To a mixture of 1750 grams of a mineral oil and 3500 grams (6.5 equivalents) of a polyisobutene-substituted succinic anhydride having an acid number of 104 prepared by the reaction of maleic anhydride with a chlorinated polyisobutene having a molecular weight of 1000 and a chlorine content of 4.5% there is added at 70 C.- 100 C. 946 grams (25.9 equivalents) of triethylene tetramine. The reaction is exothermic. The mixture is heated at 160-170 C. for 12 hours while nitrogen is passed through the mixture, whereupon 59 cc. of water is collected as the distillate. The mixture is diluted with 1165 grams of mineral oil and filtered. The filtrate is found to have a nitrogen content of 4.12%. To 6000 grams of the above acylated product there is added 608 grams (16 equivalents) of carbon disulfide at 25-50 C. throughout a period of 2 hours. The mixture is heated at 6073 C. for 3 hours and then at 6885 C./7 mm. Hg for 5.5 hours. The residue is filtered at 85 C. and the filtrate is found to have a nitrogen content of 4.45% and a sulfur content of 4.8%.

EXAMPLE 2 The product of Example 1 is heated at 150180 C. for 4.5 hours and filtered. The filtrate is found to have a nitrogen content of 3.48% and a sulfur content of EXAMPLE 3 An alkylene amine mixture consisting of 34% (by weight) of a commercial ethylene amine mixture having an average composition corresponding to that of tetraethylene pentamine, e.g., 8% of diethylene triamine, and

24% of triethylene tetrarnine (459 grams, 11.2 equivalents) is' added to 4000 grams (7.4 equivalents) of the polyisobutene-substituted succinic anhydride for Example 1 and 2000 grams of mineral oil at 6188 C. The mixture is heated at 150-160 C. for 6 hours while being purged with nitrogen. A total of 75 cc. of water is collected as the distillate during the period. The residue is diluted with 913 grams of mineral oil, heated to 160 C. and filtered. The filtrate is found to have a nitrogen content of 2.15%. To 6834 grams of the above filtrate there is added 133 grams (3.5 equivalents) of carbon disulfide at 22-30 C. throughout a period of 1 hour. The mixture is heated at 5072 C. for 2.5 hours and then to 90 C./ 15 mm. The residue is found to have a nitrogen content of 2.13% and a sulfur content of 1.41%.

EXAMPLE 4 The product of Example 3 is heated at 120-160 C. for 4 hours and filtered. The filtrate is found to have a nitrogen content of 2.14% and a sulfur content of EXAMPLE 5 A mixture-of 508 grams (12 equivalents) of Polyamine H and 152 grams (4 equivalents) of carbon'disulfide is prepared at 25 -60 C., heated to 190 C. in 3 hours and at 190-210 C. for hours. The mixture is then purged with nitrogen at 200 C. for 1 hour. The

6 residue is found to have a nitrogen content of 29.7% and a sulfur content of 6.5%. The above product grams) is added to a solution of 1088 grams (2 equivalents) of the polyisobutene-substituted succinic anhydride of Example 1 in 600 cc. of toluene at 70-80 C. in 10 minutes. The mixture is heated at 127 C. for

8 hours whereupon 10.6 cc. of Water is removed by.

azeotropic distillation with toluene. The residue is heated at 150 C. to remove toluene, diluted with 783 grams of mineral oil and heated again to 152 C./ 13 mm. The residue is found to have a nitrogen content of 1.48% and a sulfur content of 0.43%.

EXAMPLE 6 A mixture of 305 grams (8.5 equivalents) of triethylene tetramine, 102 grams (2.84equivalents) of diethylene triamine, 4000 grams (7.6 equivalents) of a polyisobutene-substituted succinic anhydride having an acid number of 106, and 2000 grams of mineral oil is prepared at 6090 C. and heated at 124-168 C. for 9 hours whereupon 71 cc. of water is removed as a distillate. The residue is diluted with 884 grams of mineral oil, heated to 160 C. and filtered. The filtrate has a nitrogen content of 2.12%. To 1500 grams of the filtrate there is added 60 grams (1.58 equivalents) of carbon disulfide at 2840 C. throughout a period of 22 minutes. The mixture is heated at 50-60 C. for 1.25 hours and then to 70 C./3 mm. Hg. The residue is found to contain 1.95% of nitrogen and 1.84% of sulfur. The amount of the carbon disulfide entering into the reaction is about one-half of the amount used in the experiment.

EXAMPLE 7 A polyisobutene-substituted succinic anhydridehaving an acid number of 101 (1200 grams, 2.16 equivalents) is hydrolyzed to the corresponding succinic acid by heating with 25 grams (2.16 equivalents) of water at 80- C. for 1 hour. To this acid there is added 223 grams (6.5 equivalents) of diethylene triamine at 70- 95 C. and 500 grams of mineral oil. The mixture is then heated to remove 47 cc. of water as the distillate, cooled to 75 C. and mixed at l02170 C. with 181 grams (4.76 equivalents) of carbon disulfide. The mixture is then heated at 170-180 C. for 1 hour diluted with 800 cc. of benzene and filtered. The filtrate is heated to C./50 mm. to remove benzene. The residue is found to have a nitrogen content of 2.94% and a sulfur content of 1.93%.

EXAMPLE 8 A mixture of 604 grams (14.8 equivalents) of the alkylene amine mixture of Example 3, 4000 grams (7.4 equivalents) of the polyisobutene-substituted succinic anhydride of Example 1 and 2000 grams of mineral oil is prepared at room temperature, then heated at 158 C. for 5 hours while being purged with nitrogen. A total of 70 cc. of water is collected as a distillate. The residue is diluted with 1013 grams of mineral oil and filtered. The filtrate has a nitrogen content of 2.73%. To 5368 grams of the filtrate there is added, throughout a period of 45 minutes, 200 grams (5.26 equivalents) of carbon disulfide at 2636 C. The mixture is heated at 90157 C. for 3.5 hours While being purged with nitrogen and filtered at C. The filtrate has a sulfur content of 1.83% and a nitrogen content of 2.45%.

EXAMPLE 9 A mixture of 602 parts (by weight) of mineral oil, 800 parts (1.48 equivalents) of the polyisobutene-substituted succinic anhydride of Example 1, and 121 parts (2.95 equivalents) of the alkylene amine mixture of Example 3 is prepared at 6082 C. heated to 150 C. in 6 hours and blown with nitrogen at 151 C. for 5 hours. A total of 15 parts of water is collected as the distillate. To the residue there is then added 56 parts (1.47 equivalents) of carbon disulfide at 143150 C. throughout 7 a period of 1 hour. The mixture is heated at 143- 150 C. for 1 hour, blown with nitrogen at 151 C. for 3 hours whereupon 25 parts of hydrogen sulfide is eliminated from the mixture. The residue is filtered, and the filtrate is found to contain 2.53% of nitrogen, 1.7% of sulfur, a basenumber of 14.7 at pH of 4 and an acid number of 1.2 at pH of 12.

EXAMPLE 10 The process of Example 1 is repeated except that the polyisobutene-substituted succinic anhydride is pre-. pared from a polyisobutene having a molecular weight of 50,000.

EXAMPLE 11 The process of Example 1 is repeated except that the polyisobutene-substituted succinic anhydride is replaced (on a chemically equivalent basis) with a polyisobentenesubstituted glutaric acid prepared by reacting dimethyl alpha-bromoglutarate with zinic and a brominated polyisobutene having a molecular Weight of 1500 and one atom of bromine per moleculerand hydrolyzing the resulting substituted ester to the corresponding glutaric acid.

EXAMPLE 13 The process of Example is repeated except that Polyamine H is replaced (on a chemically equivalent basis) with hexamethylene diamine.

' EXAMPLE 14 The process of Example 5 is repeated except that the Polyamine H is replaced (on a chemically basis) with di-propylene triamine.

EXAMPLE 15 The process of Example 5 is repeated except that the Polyamine H is replaced (on a chemically equivalent basis) with di-trimethylene triarnine.

EXAMPLE 16' The process of Example 5 is repeated except that the Polyamine H is replaced (on a chemically equivalent basis) with N-amino ethyl piperazine.

EXAMPLE 17 The process of Example 5 is repeated except that the PolyamineH is replaced (on a chemically equivalent basis) with N-amino propyl morpholine.

EXAMPLE 18 The process of Example 5 is repeated except that the Polyamine H is replaced (on a chemically equivalent basis) with N-(S-amino propyl)octadecy1amine.

EXAMPLE 19 The process of'Example 5 is repeated except that the Polyarnine H is replaced (on a chemically equivalent basis) with decamethylene diarnine. V t

The products prepared by the process illustrated abov are, for the most part, viscous liquids or semi-solids. The principal utility of such products is as additives in hydrocarbon oil compositions. When added to a hydrocarbon E acid reactant is a critical feature in determining whether the product will have detergent properties;

The amounts of the products of this invention to be used in thehydrocarbon oil depend to a large measure upon the type of the hydrocarbon oil, the degree of improvement desired in the final composition and the nature of the service to whichth'e final composition is to be subjected. The hydrocarbon oils which are benefited by the incorpation therein of the products of this invention include principally gasolines, burner fuel oils, metal working oils, cutting oils, and especially lubricating oils for use in internal combustion'engines, gears and power transmitting units. Thus, for example, for use in fuel oils, the products of this invention are usually employed in amounts ranging from 0.00=1%*to 2%, more often in the neighborhood of 0.005 %-0.5 %by weight of the final composition. For use in lubricating oils the products of this invention are employed in amounts ranging from 0.1% to 5%,more often in the neighborhood of 0.5 2%. In some instances as much as 10% or even more of the products of this invention maybe employed'in hydrocarbon oils such as lubricating compositions for marine diesel engines. 7 r

The effectiveness of the products of this invention as additives in fuel oils to inhibitthe formation of sludge is shown by the results of the fueluoil Detergent'Test (Table I). In this test a mixture of .4 liters of a catalytically cracked No. 2 light fuel oiland 15 grams of a synthetic sludge (prepared by homogenizing a /40/10, by weight, mixture of distilled Water/fuel oil/carbon black) is circulatedfor '20 hours in a fuel oil burner pump equipped with a'100-mesh Monel strainer. The sludge retained on the straineris washed with acetone and weighed. The eifectiveness of the additive is indicated by the percent reduction of the sludge retained on the strainer as compared'to the sludge formed from the fuel oil containing no additive.

Table I Sludge Composition Milligrams Percent Reduction Fuel oil 500 Fuel oil containing 25 pounds per 1,000 barrels of the product of Example 1 8 taining 0.001% of iron naphthenate and 1.5% by weight oil the products are capable of imparting corrosion inhibiting and oxidation inhibiting properties to the oil. Furthermore, the products derived from hydrocarbon substituted dicarboxylic acids ,in which t-he'hydrocarbon radical contains 50 or more aliphatic carbon atoms are capable of imparting detergent properties to the oil.

The size of the hydrocarbon substi-tuent in the succinic of the oil.

of theadditiveto be tested is heated at 300 F. for a specified period in a 2 x 15 inch boro-silicate tube. A 1.5 x 6 inch SAE 1020.steel panel is. immersed in the oil. Air is bubbled'through the oil at a rate of 10 liters per hour. The oxidized sampleis allowed to'cool to 122F. whereupon 0.5% (byvolume) of water is added and dispersed through thesample. The'sample is allowed to stand for 16 hours at room temperature and then filtered through dry' number '1 -Whatman paper (double thickness) under. slightly reduced pressure. The precipitant is Washed With naptha to constant weight and reported as milligrams of sludge percc. of oil. The steel panel is rated on a scale of 10 (no deposit on the surface) to 0 (deposit throughout the surface). The amount of sludge formed and the appearance of the steel panel are taken as indications of the detergent properties The test may be adapted to, measure also the corrosive tendency of the oilby immersing a copperlead bearing in the oil during the air-blowing step and measuring the weight loss of thebearing at the end of the test. V

Table II 1 Test Sludge Steel Bearing Composition Duration (Milli- Panel Weight (Hours) grams/100 Rating Loss,

cc. Oil) Milligrams 5 Lubricating oil 96 900-1, 200 1. Do 48 175400 1. 0 Do 1 48 850-1, 300 1-2 36-51 Lubricatigg oil pus p orglct 96 1 9 0 prepare accor mg 0 xample 1' 48 1. 7 10.0 0. 6 1() Lubricatigg oil pcllus ptrodgict 96 12 7 9 O prepare accor mg 0 x- 1 ample e8 2. 2 9. 0 5.6 Lubricating oil plus product prepared according to Example 3 96 17. 2 3. 5 Lubricating oil plus product prepared according to Example 4 96 2. 6 7.0 Lubricating oil plus product prepared according to Examp 5 48 1. 4 7.0 Lubricating oil plus product prepared according to Example s 1 4s 10. 5 7. 5 e. 0

. 1 Cu-Pb bearing used in the test.

Lubricants containing the products of this invention for use in gasoline internal combustion engines have also been evaluated by the CRC L-4545 Engine Test. The test involves the operation of a 6-cylinder gasoline automobile engine for 36 hours under the following conditions: engine speed, 3150 rpm; engine load, 30 brake horsepower; jacket coolant temperatures, outlet 200 F, inlet 190 F.; oil sump temperatures 265 F.; airzfuel ratio, 14.5 :1. The lubricant used in the engine is rated according to the weight loss of the bearing and the cleanliness of the pistons and the overall varnish and sludge deposits on the various parts of the engine. By this test a lubricant containing 1.3% by weight of the products prepared according to Example 8 gives a piston cleanliness rating of 9.4 (10 being perfectly clean) and an overall varnish and sludge rating of 96.7 (100 being perfectly clean). a

The eificacy of the products of this invention as additives in lubricating compositions for automatic transmise sions is shown by the Powerglide test (CRC designation L-39). The test consists of operating a 1955 Chevrolet Powerglide Transmission for 300hours under the following conditions: transmission sump temperature, 275 F.; governor pressure 55-70 p.s.i.; main line pressure, 8595 p.s.i.; transmission speed, 1700-1800 rpm. This test is regarded in the industry as an important means for evaluating lubricating compositions for use in automatic transmissions. The lubricant is evaluated in terms of (1) the weight loss of the cindered bronze thrust washer due to corrosion, (2) the amounts of varnish and sludge formed on the clutch plates (expressed in terms of a numerical rating from 10, representing 'no varnish or sludge, to 0, representing maximum varnish or sludge), and (3) the amounts of the overall varnish and sludge formed in the transmission (expressed as a numerical rating from 50, representing no varnish or sludge, to 0, representing maximum amounts of sludge or varnish).

A lubricating composition containing 1.5% by weight of the product prepared according to Example 9 is found to pass this test with the following results: thrust washer weight loss, 0.2%; plate varnish rating, 10.0; plate sludge rating, 10.0; overall varnish rating, 50; and overall sludge rating 50.

The eflicacy of lubricating compositions containing the products of this invention under conditions of high speed and high temperature in a diesel engine is shown by the results of a modified version of the Caterpillar CRC-L4 test (US. Army Ordinance tentative specifications AXS- 1551). The modification consists of the use of a fuel having a sulfur content of 1% (significantly higher than that of the specified fuel). In this test the lubricating composition is used in the crankcase of a 4-stroke diesel engine having a 5%" x 8" stroke and a compressionratio of 15 to 1, operated for hours under the following conditions: speed, 100 rpm; B.t.u. input per minute, 2900-3000; load, 20 brake horsepower; water jacket outlet temperature, 175 -180 F.; oil temperature, -150 F. The lubricating composition is evaluated in terms of (1) the piston cleanliness expressed as a numerical rating of 0-100, 100 being perfectly clean and 0 representing maximum deposit and (2) percent ring filling. A lubri eating composition containing 0.57% by weight of the product prepared according to Example 3 is found to pass this test with the following results: ring filling of 1% and a piston cleanliness of 97.

This invention contemplates alsothe use of other additives in lubricating compositions containing the products prepared by the process described herein. Such additives includes, for example, detergents for both ash-con taining and 'ashless types, extreme pressure addition agents, rust inhibiting agents, vicosity index improving agents, pour point depressing agents, anti-foam agents and supplemental oxidation and corrosion inhibiting agents. A particular effective combination of additives for use in lubricating oils for internal combustion engines, gears and power transmitting units comprising the products prepared by the process of this invention and an ash-containing detergent. The detergent may be either a neutral salt or a basic salt of alkali or alkaline earth metals with oil-soluble sulfonic acids, carboxylic acids or organic phosphorus acids, such as prepared by the reaction of an olefin polymer with a phosphorus sulfide. The basic salts of alkaline earth metals with sulfonic acid or organic phosphorus acid derived from olefin polymers having molecular weight above about 700 are especially effective for use in such lubricating compositions. The term basic salts designates the metal salts in which the metal is present in stoichiometrically larger amounts than the organic acid radical.

A commonly used method for preparing the basic metal salt involves heating an oil-soluble acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, metal hydroxide, metal carbonate, metal sul fide, or the like and filtering the resulting mixture in a diluent such as mineral oil to produce a fluid product. The use of a promoter compound in neutralization step is likewise well known in the art. The compounds useful as the promoter include phenolic compounds such as phenol, naphthol, alkylphenols, and alkylnaphthols; alcohols such as methyl alcohol, butyl alcohol, ethylene glycol, Cellosolve, carbitol, decyl alcohol, and oleyl alcohol; amines such as aniline, phenyl-beta-naphthyl amine, phenothiazine, and phenylenediamine. A particularly effective method for preparing the basic salt comprises carbonating a mixture of an oil-soluble acid, e.g., mahogany acid, with a stoichiometric excess of an alkaline earth metal neutralizing agent in the presence of a phenolic promoter or an alcohol promoter at a temperature above about 50 C., preferably between 80 C. and 200 C. The following examples illustrate the method by which basic salts may be prepared.

EXAMPLE A A mixture of 590 parts of a mineral oil, 110 parts of water, 61 parts of heptylphenol, 340 parts of barium mahogany sulfonate, and 227 parts of barium oxide is heated at 100 C. for 0.5 hour and then to C. Carbon dioxide is then bubbled into the mixture until the mixture is substantially neutral. The mixture is filtered and the filtrate found to have a sulfate ash content of 25%. v A

.. EXAMPLE B A polyisobutene having a molecular weight of 50,000 is mixed with 10% by weight of phosphorus pentasulfide at 200 C. for 6 hours. The resulting product is hydro- 1 l. lyzed by treatment with steam at 160 C(to produce an acidic intermediate. The acidic intermediate is then converted to a basicsalt by mixing with 2 moles of barium hydroxide and 0.7 mole of phenol and carbonating the mixture at' 150 C. to produce a fluid product.

In lieu of the acids illustrated in the above examples other acids which may be used include oil-soluble sulfonic acids preparedby sulfonating monoor poly-alkylated aromaticrhydrocarbons such as di-dodecyl benzene, with sulfuric acid, sulfur trioxide, chlorosulfonic acid, oleum, etc.: organicphosphorus acids prepared by the reaction of an olefin polymer with phosphorus trichloride and sulfur, phosphorothioic chloride, phosphorus heptasulfide, white phosphorus and sulfur halide, etc. In lieu of the barium neutralizing agent illustrated in the above examples, other alkaline earth metal neutralizing agents useful herein are illustrated by magnesium hydroxide, cal cium oxide, calcium hydride, barium methylate, stron tium hydroxide, or the like. 'When used with the products of this invention in lubricating compositions, the ash-containing detergents are usually present in amounts to impart from about 0.1% to 10% by weight of sulfate ash to the composition The extreme pressure addition agents useful in lubricating compositions containing products of this invention are illustrated by halogenated hydrocarbons such as chlorinated wax; organic sulfides and, polysulfides such as dibutyl tetrasulfide, benzyl disulfide, di-(chlorobenzyl) disulfide, sulfurized methyl oleate, sulfurized sperm oil, .sulfurized lard oil, sulfurized dipentene and sulfurized turpentine; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine, dipentene, sperm oil, lard oil, or methyl oleate. Corrosion and oxidation inhibiting agents are exemplified by metal dialkyl phosphorodithioates, metal dialkaryl phosphorodithioates, metal dialkyl carbamates, metal salts of sulfurized alkyl-phenols, organic phosphorus acid esters such as dior tri-hydrocarbyl phosphites, etc. Specific examples of such inhibitors include: zinc ,dioctyl phosphorodithioate, zinc butylcyclohexyl phosphorodithioate, barium dinonyl phosphorodithioate, zinc diheptylphenyl phosphorodithioate, zincdioctylicarbamate, barium salt of bis (hydroxylphenyl) sulfide, calcium salt of bis(hydroxylphenyl) methane,'dioctyl phosphite, didodecyl phosphite, tricresyl phosphite, etc. .The extreme. pressure agents and. the inhibitors are usually present in lubricating compositions in amounts within the range from about 0.05% to 5% by weight. The following examples illustrate the use of the prodnets of this invention with other additives in lubricating compositions. These lubricating compositions are adapted especially for use as lubricants for internal combustion engines, gears, and/orpower transmitting units including especially automatic transmissions for passenger automobiles (all parts are by weight).

Lubricating composition 1: Parts SAE 20 mineral oil 100 Product of Example 1 0.2 Barium detergent of Example A 5 Lubricating composition'Il:

SAE W-30 mineral oil 100 Product of'Example 9 1 f Barium detergent of'Example'B 3 Lubricating composition III: SAE 30 mineral oil 100 Product of Example 8 1.5 Sulfurized sperm oil having a sulfur content of a 10% 2 Lubricating composition IV:

SAE 50 mineral oil 100 Product of Example 6 0.15 Bariumdetergent of Example A 7 .5 Didodecyl phosphite 0.2 Poly(alkyl siloxane) anti-foam agent 0.2

l2 Lubricating composition V:

SAE -5W-10mineral oil 100 Product of Example 9 2 Calcium mahogany sulfonate 2.5 Zinc di-cyclohexyl phosphorodithioate 0.75 Lubricating composition VI: I

SAE 1'0W-30 mineral oil 100 Product of Example 2 0.5 Neutral Barium salt of an acidic composition prepared by the reaction of polyisobutene having a molecular weight of 1000 with PCl and sulfur 10 Lubricating composition VII:

SAE W mineral oil Product of Example 4 3 Chlorinated eicosane having a chlorine content of 40% 5 Dibutyl' tetrasulfide 2 Reaction product of P 8 with methyl oleate 2.5 Zinc dihexylphenyl phosphorodithioate 1 'Whatis'claimed is:

1. A process for preparing sulfur and nitrogen-containing compositions which comprises reacting, at a temperature above about 80 C. and below the decomposition temperature,-1.0 mole ofan alkylene amine having up to about 8 carbon atoms in the alkylene radical with at least about 0.5 equivalent of carbon disulfide and at least about 1 equivalent of ahydrocarbon-substituted-dicarboxylic acid having at least about 12 aliphatic carbon atoms in the hydrocarbon radical, the total number of nitrogen radicals in said' alkylene amine being at least as great as the total number of equivalents of carbon disulfide and said dicarboxylic acid, and removing the water formed by the reaction.

2. The process of claim 1 characterized further in that the alkylene amine is an ethylene amine.

. 3. The process of claim 1 characterized further in that the hydrocarbon-substituted dicarboxylic acid is a hydrocarbon-substituted succinic acid.

4*. The process'of claim 1 characterized further in that the hydrocarbomsubstituted dicarboxylic. acid is a hydrocarbon-substituted succinic acid anhydride wherein the hydrocarbon radical is derived :from a'substantially aliphatic olefin polymer. 7 3 5. The process of claim 1 characterized further in that the hydrocarbon-substituteddicarboxylic acid is a hydrocarbon-substituted succinic acid anhydride wherein the hydrocarbon radical'is derived from a substantially aliphatic polymer of isobutene having a. molecular weight within the range of to 2000. v

6. The process of claim 1 characterized further in that the ratio of equivalents of the carbon disulfide used to the hydrocarbon-substituted dicarboxylic acid used is between 1:3 to 3:1.

7. A process for preparing sulfur and nitrogen-containing compositions which comprises acylating, at a temperature above about 80 C. and below the decomposition temperature, 1.0 mole of an alkylene amine having up to about 8 carbon atoms in the alkylene radical with at least about 1 equivalent'of a hydrocarbon-substituted dicarboxylicacid having at least about 12 aliphatic carbon atoms in the-hydrocarbon radical, removing the water formedthereby and reacting the acylated amine with at least about 0.5 equivalent of carbon disulfide, the total number of nitrogen radicals in said alkylene amines being at least as great as'the total number of equivalents of carbon disulfide andsaid dicarboxylic acid.

8. A process of claim 7 characterized further in that the step of reacting the acylated amine with carbon disulfide is carried out at atemperatureabove about 25". C. and below about 70 C.

9. The process of claim ,7 characterized furtherin that the step of reacting the a'cylated amine with carbon disulfide is carried out at a temperature above'about 70 C 10. The process of claim 7 characterized further in that the alkylene amine is an ethylene amine.

11. The process of claim 10 characterized further in that the ethylene amine is a mixture of ethylene amines having an average composition corresponding to that of tetraethylene pentamine.

12. The process of claim 10 characterized further in that the ethylene amine is diethylene triamine.

13. A process for preparing sulfurand nitrogen-containing compositions which comprises acylating, at a temperature above about 100? C. and below the decomposition point, 1.0 mole of an ethylene amine with at least about 1.0 equivalent of a hydrocarbon-substituted succinic acid anhydride wherein the hydrocarbon radical is derived from a substantially aliphatic polymer of a lower mono-olefin having a molecular weight above about 700, removing the water formed thereby and reacting the acylated amine with at least about 1 equivalent of carbon disulfide at a temperature above about 25 C., the total number of nitrogen radicals in said ethylene amine being at least as great as the total number of equivalents of carbon disulfide and said succinic acid anhydride.

14. The process of claim 13 characterized further in that the hydrocarbon-substituted succinic acid anhydride is a polyisobutene-substituted succinic acid anhydride wherein the polyisobutene radical has a molecular weight of about 1000.

15. A process for preparing sulfurand nitrogen-containing compositions which comprises acylating, at a temperature above about 100 C. and below the decomposition point, 1.0 mole of an ethylene amine with at least 5 about 1.0 equivalent of a hydrocarbon-substituted succinic acid anhydride wherein the hydrocarbon radical is derived from a substantially aliphatic polymer of a lower mono-olefin having a molecular weight above about 700, removing the water formed thereby and reacting the acylated amine with at least about 1 equivalent of carbon disulfide at a temperature above about 25 C., the combined equivalents of said dicarboxylic acid and said carbon disulfide being approximately equal to the number of equivalents of ethylene amine.

16. The product of the process of claim 1.

17. The product of the process of claim 14.

References Cited by the Examiner UNITED STATES PATENTS 688,885 12/01 Ris 260-132 1,981,055 11/34 Linster et a1. 260-135 2,278,762 4/42 Bergen 25247.5 2,317,751 4/ 43 Frolich et al 25247.5

25 CHARLES B. PARKER, Primary Examiner.

JULIUS GREENWALD, DANIEL D. HORWITZ,

Examiners. 

1. A PROCESS FOR PREPARING SULFUR- AND NITROGEN-CONTAINING COMPOSITION WHICH COMPRISES REACTING, AT A TEMPERATURE ABOVE ABOUT 80*C. AND BELOW THE DECOMPOSITION TEMPERATURE, 1.0 MOLE OF AN ALKYLENE AMINE HAVING UP TO ABOUT 8 CARBON ATOMS IN THE ALKYLENE RADICAL WITH AT LEAST ABOUT 0.5 EQUIVALENT OF CARBON DISULFIDE AND AT LEAST ABOUT 1 EQUIVALENT OF A HYDROCARBON-SUBSTITUTED DICARBOXYLIC ACID HAVING AT LEAST ABOUT 12 ALIPHATIC CARBON ATOMS IN THE HYDROCARBON RADICAL, THE TOTAL NUMBER OF NITROGEN RADICALS IN SAID ALKYLENE AMINE BEING AT LEAST AS GREAT AS THE TOTAL NUMBER OF EQUIVALENTS OF CARBON DISULFIDE AND SAID DICARBOXYLIC ACID, AND REMOVING THE WATER FORMED BY THE REACTION. 